1. Field of the Invention
The present invention relates to a process for efficiently preparing a syndiotactic polymer of an unsaturated carboxylic acid ester (i.e., unsaturated carboxylate) such as (meth) acrylate having a narrow molecular weight distribution and a high molecular weight, and a block copolymer of an .alpha.-olefin such as ethylene with an unsaturated carboxylate.
2. Description of the Related Art
In the prior art, as the known technique for the preparation of polyacrylates having narrow molecular weight distributions, many processes are known which concern an anion polymerization with the use of an alkali metal and an alkaline earth metal compound. For example, when lithium is used as the initiator in liquid ammonia, one with a relatively narrower molecular weight distribution of Mw/Mn=1.5 can be obtained (W. E. Good, J. Polym. Sci., 42, 367, 1960), and when 1,1-diphenylhexyllithium is used, a polymethyl methacrylate wherein Mw/Mn=1.18 can be obtained (H. Hatada, Kobunshi Ronbunshu, 43, 857, 1986). Further, also with a Grignard reagent, a polymethyl methacrylate wherein Mw/Mn=1.2 can be obtained, but the narrowness of the molecular weight distribution and the syndiotacticity obtained are not satisfactory.
As the method of preparing a polyacrylate with an extremely narrow molecular weight distribution, there are known the method using sodium-biphenyl (A. Roig, J. Polym. Sci., B3, 171, 1965) and the method using aluminum-poephyrin (Japanese Unexamined Patent Publication (Kokai) No. 1-259008), but these involve problems such that the molecular weight of the polymer obtained is small, the polymerization rate is slow, and an expensive polar solvent must be used.
Yasuda and Nakamura et al. have reported that a syndiotactic polymethyl methacrylate having a high molecular weight with a relatively lower molecular weight distribution can be obtained by using a lanthanide divalent compound as the initiator (Chemical Society of Japan, 58th Anniversary Meeting Pre-text I, 1 II B07, 1989). The polymerization using a lanthanide divalent compound as the initiator is attracting attention because it is a living polymerization, and because a polymer with a relatively narrower molecular distribution can be obtained.
Nevertheless, the polymethyl methacrylate formed with the above-mentioned lanthanide divalent compound is not very narrow, i.e., about Mw/Mn=1.2, and the initiator efficiency remains as low as 25%. Also, the lanthanide divalent compound alone has no olefin polymerization activity, and no polymerization initiation ability for an acrylate.
The copolymer of a polymethacrylate and a polyolefin may be considered to have an excellent adhesiveness, printability, and compatibility with other polymers, but an efficient method of synthesizing same is not known. Japanese Unexamined Patent Publication (Kokai) No. 59-43003, proposed a method of copolymerizing propylene with an unsaturated carboxylate, using TiCl.sub.4 and Al(C.sub.2 H.sub.5).sub.3 as the catalyst in the presence of a Lewis acid, and Japanese Unexamined Patent Publication (Kokai) No. 64-14217, proposed a copolymerization of ethylene with an unsaturated carboxylate using a zero valent nickel chelate compound and aluminoxane, but these methods involve problems such that a large amount of Lewis acid is required, or a large amount of aluminoxane of the co-catalyst is required.